Electroanalytical

J. F. Rusling, in Electrochemistry in Micelles, Microemulsions and Related Microheterogeneous Fluids, Electroanalytical Chemistry, A Series of Advances, Marcel Dekker, New York, 1994. 

Osteryoung J and O Dea J J 1986 Square wave voltammetry Electroanalytical Chemistry ed A J Bard (New York Dekker)... 

Vassos, B. H. Ewing, G. W. Electroanalytical Chemistry. Wiley-Interscience New York, 1983. 

Wang, J. Electroanalytical Techniques in Clinical Chemistry and Eaboratory Medicine. VCH New York, 1998. 

Curran, D. J. Constant-Current Coulometry. Chapter 20 in Kissinger, P. T. Heineman, W. R., eds. Eaboratory Techniques in Electroanalytical Chemistry. Marcel Dekker, Inc. New York, 1984, pp.539—568. 

Laboratory Techniques in Electroanalytical Chemistry. Marcel Dekker, Inc. New York, 1984, pp. 569-607. 

Electroanalytical chemistry is one of the areas where advantage of the unique properties of SAMs is clear, and where excellent advanced analytical strategies can be utilized, especially when coupled with more complex SAM architectures. There are a number of examples where redox reactions are used to detect biomaterials (357,358), and where guest—host chemistry has been used to exploit specific interactions (356,359). Ion-selective electrodes are an apphcation where SAMs may provide new technologies. Selectivity to divalent cations such as Cu " but not to trivalent ions such as Fe " has been demonstrated (360). 

Ion Selective Electrodes Technique. Ion selective (ISE) methods, based on a direct potentiometric technique (7) (see Electroanalytical techniques), are routinely used in clinical chemistry to measure pH, sodium, potassium, carbon dioxide, calcium, lithium, and chloride levels in biological fluids. 

Electrochemical cells may be used in either active or passive modes, depending on whether or not a signal, typically a current or voltage, must be actively appHed to the cell in order to evoke an analytically usehil response. Electroanalytical techniques have also been divided into two broad categories, static and dynamic, depending on whether or not current dows in the external circuit (1). In the static case, the system is assumed to be at equilibrium. The term dynamic indicates that the system has been disturbed and is not at equilibrium when the measurement is made. These definitions are often inappropriate because active measurements can be made that hardly disturb the system and passive measurements can be made on systems that are far from equilibrium. The terms static and dynamic also imply some sort of artificial time constraints on the measurement. Active and passive are terms that nonelectrochemists seem to understand more readily than static and dynamic. 

From an electroanalytical point of view, the double-layer capacitance is a nuisance resulting in the charging current, which has no analytical value. 

Active electrochemical techniques are not confined to pulse and linear sweep waveforms, which are considered large ampHtude methods. A-C voltammetry, considered a small ampHtude method because an alternating voltage <10 mV is appHed to actively couple through the double-layer capacitance, can also be used (15). An excellent source of additional information concerning active electroanalytical techniques can be found in References 16—18. Reference 18, although directed toward clinical chemistry and medicine, also contains an excellent review of electroanalytical techniques (see also... 

Perhaps the most precise, reHable, accurate, convenient, selective, inexpensive, and commercially successful electroanalytical techniques are the passive techniques, which include only potentiometry and use of ion-selective electrodes, either direcdy or in potentiometric titrations. Whereas these techniques receive only cursory or no treatment in electrochemistry textbooks, the subject is regularly reviewed and treated (19—22). Reference 22 is especially recommended for novices in the field. Additionally, there is a journal, Ion-Selective Electrode Reviews, devoted solely to the use of ion-selective electrodes. 

The reference electrode contributes heavily to the economics of electroanalytical chemistry. Companies that sell and service electroanalytical instmmentation are few in number and small in size, or they are parts of much larger companies. One suppHer of electroanalytical instmmentation is Princeton AppHed Research Corp. (PARC) of Princeton, Newjersey. PARC is a subsidiary of EG G Instmments, Inc. Among the many suppHers of ion-selective electrodes are Orion (Boston, Massachusetts), Corning (Corning, New York), and Ingold (Wilmington, Massachusetts). Brinkmann Instmments, Inc. (Westbury, New York) is a useful suppHer of titration equipment. 

J. E. Harrar, "Techniques, Apparatus, and Analytical AppHcations of ControUed-Potential Coulometry," in A. J. Bard, ed., Electroanalytical Chemisty, Vol 8, Marcel Dekker, New York, 1975. 

J. Wang, Electroanalytical Techniques in Clinical Chemistry andEaboratoy Medicine, VCH, New York, 1988. 

Precise kinetic electroanalytical data permit to describe quantitatively the kinetics of the whole process with a precision that has never been achieved before by patch-clamp techniques or spectroscopic near-field methods. This enables to investigate finely these events and to identify the exact physicochemical nature of all the individual physicochemical and biological factors which concur to produce vesicular release. 

Electroanalytical Chem. Proc. ElectrofinnAnalysis hit. Conf. Electroanal. Conf. Electroanal. Chem. J. 1988, 373 (1990). 

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